10.1021/ja304049x.s001 Qing Guo Qing Guo Chenbiao Xu Chenbiao Xu Zefeng Ren Zefeng Ren Wenshao Yang Wenshao Yang Zhibo Ma Zhibo Ma Dongxu Dai Dongxu Dai Hongjun Fan Hongjun Fan Timothy K. Minton Timothy K. Minton Xueming Yang Xueming Yang Stepwise Photocatalytic Dissociation of Methanol and Water on TiO<sub>2</sub>(110) American Chemical Society 2012 BBO calculation photocatalytic methanol dissociation Stepwise Photocatalytic Dissociation Theoretical TiO H 2O photocatalytic dissociation CD 2O Ti 5c sites recombination photocatalytic water splitting CD 3OH H 2O photocatalysis 2012-08-15 00:00:00 Journal contribution https://acs.figshare.com/articles/journal_contribution/Stepwise_Photocatalytic_Dissociation_of_Methanol_and_Water_on_TiO_sub_2_sub_110_/2496193 We have investigated the photocatalysis of partially deuterated methanol (CD<sub>3</sub>OH) and H<sub>2</sub>O on TiO<sub>2</sub>(110) at 400 nm using a newly developed photocatalysis apparatus in combination with theoretical calculations. Photocatalyzed products, CD<sub>2</sub>O on Ti<sub>5c</sub> sites, and H and D atoms on bridge-bonded oxygen (BBO) sites from CD<sub>3</sub>OH have been clearly detected, while no evidence of H<sub>2</sub>O photocatalysis was found. The experimental results show that dissociation of CD<sub>3</sub>OH on TiO<sub>2</sub>(110) occurs in a stepwise manner in which the O–H dissociation proceeds first and is then followed by C–D dissociation. Theoretical calculations indicate that the high reverse barrier to C–D recombination and the facile desorption of CD<sub>2</sub>O make photocatalytic methanol dissociation on TiO<sub>2</sub>(110) proceed efficiently. Theoretical results also reveal that the reverse reactions, i.e, O–H recombination after H<sub>2</sub>O photocatalytic dissociation on TiO<sub>2</sub>(110), may occur easily, thus inhibiting efficient photocatalytic water splitting.